Developable azo dyes and process of producing the same on the fiber



Patented July 4, 1939 UNITED STATES PATENT OFFICE DEVELOPABLE AZO DYES AND PROCESS OF PRODUCING THE SAME ON THE FIBER Swanie Siguard Rossander, Wilmington, Del., assignor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware . No Drawing. Application November 20, 1937,

Serial No. 175,641

11 Claims.

wherein Alk designates the bivalent residue of a saturated hydrocarbon, forlnstance a paraflin hydrocarbon having from 2 to 18 carbon atoms or a cyclo paraffin hydrocarbon; R stands for a divalent radical of the benzene series, such as benzene or its alkyl, alkoxy or halogen substitution products; the N=N groups are meta or para to the CONH' groups on the benzene nuclei and R1 and R2 designate azo dye coupling components which contain water-solubilizing groups, such as sulfo or car-boxy, and which contain further a primary amino group. The water-solubilizing groups impart to my novel dyestuffs substantivity toward vegetable fiber, while the amino groups enable these dyestufis to be developed on the fiber by tetrazotization and coupling to water-insolubilizing components, whereby the dyeings become fast to washing.

The preparation of dyestufis of the above general formula is more fully described in my copending application, Ser. No. 175,640, filed simul taneously herewith. My present application is concerned more particularly with the details of development on the fiber, and with the form of the dyestulf on the fiber when so developed.

By cellulosic fiber in this discussion I have in mind the usual textile fibers of vegetable origin and composed principally of cellulose such as cotton or regenerated cellulose.

As typical illustrations of Alk in the above general formula may be mentioned the divalent radical of ethane, hexane, decane or cyclohexane. As typical illustrations of R may be mentioned benzene, and its methyl, ethyl, ,methoxy, .ethoxy, chloro or bromo substitution derivatives. As typ ical coupling components R1 and R: which may be alike or different, may be mentioned the aminonaphthol-sulfonic acids, the amino-aroylaminonaphthol-sulfonlc acids, and the aminoaryl-pyrazolone-carboxylic acids.

As suitable developing components after tetrazotization on the fiber may be mentioned the naphthols, the aryl-methyl-pyrazolones, the aceto-acetarylids, the meta-phenylene-diamines, or any other developer of. those customarily employed in the art and having no water-solubiliz- 5 ing groups.

After development on the fiber, the novel com,- pounds of my invention possess the general structure indicated by the following formula YHD wherein X stands for a di-(amino-aroylamino) derivative of a saturated hydrocarbon which can be tetrazotized and coupled to coupling compoments; Y1 and Y2, which may be the same or different, represent coupling components each of which contains a free amino group which, after coupling, is capable of further diazotization and coupling. Either or both of Y1 and Y2 may contain a solubilizing group such as carboxylic acid or sulfonic acid; D may be a developing agent of the benzene, naphthalene, pyrazolone or acetoacetarylide series, which does not contain a solubilizing group such as carboxylic or sulfonic acid.

Without limiting my invention to any particular procedure, the following examples are given to illustrate my preferred mode of operation. Parts mentioned are by weight.

Example I Five parts ofcotton piece goods is dyed by 'immersion into a solution of ten-hundredths parts of the disazo dye obtained by coupling tetrazotized di-(p-aminobenzoyl) -ethylene-diamine into two molecules of p-aminobenzoyl-J acid, in approximately 500 cc. water. The solution is maintained at to 212 F. for hour; salt being slowly added to exhaust the dyestufi. The dyed fabric is rinsed in cold water and put in 200 parts of water at 20 G. Add three-tenths parts of sodium nitrite and four-tenths parts of sulfuric acid. Stir 15 minutes. Rinse with. cold water. Dissolve 45 one-tenth part of beta-naphtha] in 200 parts water and one-twentieth part of caustic soda. Stir the solution rapidly while adding the above rinsed piece goods. Stir 15 minutes. Rinse in cold water and dry. The dyeing is a bright orange shade to of outstanding fastness to washing. The probable formula of the dye on the fiber is In a similar manner other dyes of the series disclosed in my copending application of even date, Ser. No. 175,640, may be developed on the fiber into the corresponding tetrakosazo or polyazo dyestufis or outstanding fastness to washing.

In the following table are given a number of dyestufl's actually prepared by me together with their shade on the fiber. In this table, the symbol PAB stands for para-aminobenzoyl; MAB, for meta-aminobenzoyl".

SOiNa ing component which is free of water and solubilizing groups.

OzNa N il-Q0 ONH OH: H i

I H: =NC C ONE Dyestufi in substance Shade on cotton Developed withor regenerated Tetrazo component oi Coupled to two moles ofcellulose Di-(PAB)-ethylene-diamlne PAB-J-acid Beta-'naphthol Orange.

Do l-phenyI-3-methyl-5-pyrazolone Yellow orange.

Do Acetoacetanilide Do.

D Meta-tolylene-diamine Red orange. Di-(PAB)-decamethylene-diamine.- Bordeaux.

Do Orange. Di-(PAB)-decamethylene-diamineno.

Do D0.

D0 Red. Di-(gdfABydecamethylene-diaminm Orange.

ic-a Di-(PAB)-ethylenem I-acid do Bordeaux. -Do MAB-.T-acid do i Orange. Do l-rlneta gmino-phenyl-5-pyrazolone-3-carboxyll-phenyl-3-methyl-5-pyrazolone Yellow.

Do ..do Beta-naphthol Orange. Di-(PAB)-ethylene-dlamine. Di-(PAB)-3,5-d1amino-benzoyl-J-acid do Do. Di-(MAB)-ethylene-dlamine .l-acid Bordeaux.

D0. MAB Orange.

Do- PAB-J-acid Do.

Do (in l-phenyl thyl\5-pyrazolone Yellow. Di-(PAB)-cyc1ohexy1diamiue. J-aeid Beta-naphthol Bordeaux.

D0 PAB-J-acid do. Orange.

Do l-rinetai-gmino-phenyl-5-pyrazolone-3carboxyldo Do.

e-ac D0 l-phenyl\'i-methyl-5-pyrazolone Yellow.

It will be understood that the details of procedure may be varied within the skill of those engaged in this art, without departing from the spirit of this invention.

I claim:

1. An azo dye of the general formula All:/

NHCO-RN=N-R,N=NRa wherein Alk stands for the bivalent radical 01' a saturated hydrocarbon having from 2-18 carbon atoms, R stands for a divalent aryl radical of the benzene series, the two valences of R being in a position selected from the group consisting of meta and para, R1 and R2 stand for azo-dye coupling components which contain water-solubilizing groups, and R3 stands for an azo-dye developdeveloping component which is free of water solubilizing groups.

3. An azo dye of the general formula wherein the N=N- groups being attached to the benzene nucli in meta or para positions relative to the NHCO groups R1 stand for an azodye coupling component which possesses a watersolubilizing group, while R3 stands for an azodye developing component which is free of watersolubilizing groups.

4. The azo dye corresponding to the formula Di (para-aminobenzoyl) ethylene-diamine 3 Paraaminobenzoyl-J-acid I, beta-naphthol wherein the arrows f; stand for the expression tetrazotized and coupled to two moles of.

5. The azo dye corresponding to the formula Di (para-aminobenzoyl) ethylene-diamine I 1-meta-aminophenyl-5-pyrazolone 3-carboxylic acid: 1-phenyl-3-methyl 5-pyrazolone wherein the N=N groups being attached to the benzene nuclei in meta or para positions relative to the NHCO groups R1 and R2 designate azo-dye coupling components each of which contains a primary amino group and a water-solubilizing group; tetrazotizing the said compound on the fiber, and further coupling the same with an azo-dye developing component which is free of water-solubilizing groups.

9. The process of dyeing cellulosic material which comprises applying thereto an azo dye of the general formula wherein the arrows I, stand for the expression tetrazotized and coupled to two moles of.

6. The azo dye corresponding to the formula Di (para-aminobenzoyl) ethylene-diamine 3 J acid I, beta-naphthol wherein the arrows 3 stand for the expression tetrazotized and coupled to two moles of.

7. The process of dyeing cellulosic material which comprises applying thereto an azo dye of the general formula wherein Alk stands for the bivalent radical of a saturated hydrocarbon having from 2-18 carbon atoms, the two valences of B. being in a position selected from the group consisting of meta and para, R stands for a divalent aryl radical of the benzene series, and R1 and R2 designate azodye coupling components each of which contains a primary amino group and a water-solubilizing group; tetrazotizing the said compound on the fiber, and further coupling the same with an azodye developing component which is free of water solubilizing groups.

8. The process of dyeing cellulosic material which comprises applying thereto an azo dye of the general formula wherein R1 designates an azo-dye coupling component containing a primary amino group and a water-solubilizing group; tetrazotizing the said compound on the fiber, and coupling the same with 1-phenyl-3-methyl-5-pyrazolone.

11. The process of producing a polyazo dye which comprises tetrazotizing a compound of the general formula All:

SWANIE SIGUARD ROSSAN DER. 

